Method for the separation of chemically modified rosin alcohols into components



Patented Feb. 24, 1942 METHOD FOR THE SEPARATION OF CHEMI- CALLY MODIFIED ROSIN ALCOHOLS INTO COMPONENTS Joseph N. Borglin, Wilmington, Del., assignor to Hercules Powder Company, Wilmington, DeL, a corporation of Delaware No Drawing. Original application September 28,

1939, Serial No. 296,946. Divided and this application July 10, 1941, Serial No. 401,795

2,274,523 OFFICE l Claims.

This invention relates to a method for the separation of alcohol derivatives of chemically modified rosins into components, and more particularly the separation of alcohol derivatives of chemically modified rosins into components by treatment with a selective solvent.

Due to the complexity of the chemical structure of rosin, treatments for the production of chemical modification practically always re- .sult in products which are mixtures of two or more chemical compounds. The product may contain unchanged rosin or the rosin may be converted into two or more different materials, or both. The esterification of such a modified product produces a modified rosin ester which, in lective solvent. This process can be repeated as similarly, is a mixture of chemically difierent a y times as necessary o Produce the desired esters. Likewise, esterification of rosin and then separation of the components. treatment to produce chemical modification, n Carrying o this method, the alcohol gives a product which is a mixture of chemically Va VeS o the d fi d rosins may or may not different esters. Similarly, treatment of the an be first dissolved in a solvent therefor which is modified rosin to produce an alcohol derivative immiscible With the Selective Solvent Which is thereof, gives analcohol which is amixture of used. Ordinarily, it will be found convenient the resin alcohols derived from th ompon t to use such .a solvent, particularly if the alcohol 0f the modified rosin material; Likewise treatderivative of the modified rosin treated is a solid ment of rosin to produce an alcohol d th n at the temperature of treatment. When it is chemical modification of the rosin a1c ho1 by th desired to use a solvent for the alcohol derivative procedures utilized in chemically modifying the of the fi d rosin, e procedure in drosin produces a similar mixture of chemically nce w th s invention w s t of d sdifferent resin alcohols. I solving the alcohol derivative of the modified ros- Thus, for example, the hydrogenation of rosin in in the Solvent, Contacting the Solution so may result in a mixture of u ch n d rosin and formed with a selective rosin color body solvent dihydro-rosin. More complete hydrogenationreimmiscible therewith, Separating e Wo S usults in a mixture of dihydro-rosin and tetrahytime h formed, and recovering a Component dro-rosin. The production of a product which is of the alcohol derivative of the modified rosin entirely tetrahyd-ro-rosin has so far proved imfrom each Solution e eimple, by evappossible. The esterification of a hydrogenated orotins t sp t v s ts, p a y u r rosin results in a. mixture of rosin esters. Liked pressure This procedure y be wise, the hydrogenation of rosin esters results Deated as many times as desiredin a mixture of ordinary rosin ester and dihydro- After Separating e alc de vat ve f the rosin ester or a mixture of dihydro-rdsin ester modified rosin into components by the above. and tetrahydro-rosin ester. Similar mixtures procedure, each p e t may be further D exist in the alcohol derivatives of the hydrofied by crystallization from suitable solvents. genated rosin. fractionation under reduced pressure, contact- The separation of the chemically diflferent ing' with an absorbent, such as fullers earth, components of the chemically modified rosins or kieseigu-hl, activated carbon of the ester and alcohol derivatives oi such rosins The alcohol derivative a modified rosin has heretofore been practically impossible, and which I y treat n accordance With s the various commercial products h v b vention may be an alcohol derivative of any rosin plex mixtures ofcompounds of different chem.i. which. has been treated to m d y its chemical cal structure. No successful method'for sepstructure so vthat the resultant product s a arating the components of h i t has mixture of two or more chemically different subbeen developed, in spite of the fact that it has stonoos- The hydrogenation of rosin in the been fully realized that such separation would be presence of a suita c ys according to m of great value from a commercial standpoint, as s known to the art produces Such a modified well as from a sci ntifi ta d i t, 35 rosin. The treatment of a hydrogenated rosin Now, I have found that I can separate alcohol o Produce an alcohol derivative, likewise, P der vatives of chemically modified rosins into duces an alcohol which is a mixture of the resin their components by a method which is relaalcohols derived from the different components tlvely simple, efiicient and adaptable to comof the hydrogenated rosin as well as non-alcomerclal operation. I accomplish this by treatholic impurities present. Similarly. hydrogenaing an alcohol derivative of chemically modified rosin with a substance selected from the group of substances now known to the art to be selective solvents for the visible and latent color bodies of rosin.

The process in accordance with this invention consists of treating an alcohol derivative of a tion of a rosin alcohol gives a mixture of two or more chemically different substances. The alcohol derived from hydrogenated wood rosin, for example, may contain dihydroabietyl alcohol and tetg'sahydroabietyl alcohol among other constituen The polymerization of rosin to increase its molecular weight and melting point by treatment with a polymerizing agent, for example, volatile metal halides, as, boron trifiuoride, zinc chloride, stannic chloride, aluminum chloride, ferric chloride; mineral acids, as, sulfuric acid, phosphoric acid; fullers earth; hydrogen fluoride; acid salts, as sodium acid sulfate, etc.; metallic silicon; hydro fluoro-boric acid; etc., according to methods known to the art, produces such a modified rosin. The treatment of the polymerized rosin to produce an alcohol derivative, for example, hydrogenation, produces an alcohol which is a mixture of the resin alcohols derived from the different components of the polymerized rosin as well as non-alcoholic impurities present. Similarly, polymerization of a rosin alcohol gives a mixture of two or more chemically different substances.

Again, the treatment of rosin with a suitable catalyst, as, for example, a hydrogenation catalyst, as nickel, nickel chromite, platinum, palladium, etc., at an elevated temperature of, for

' example, from about 150 C. to about 200 C. and

without reaction between the rosin and any added substance, to produce an intraand intermolecular rearrangement within the hydrocarbon nucleus of the rosin with a reduction in the apparent unsaturation as disclosed in U. S. Patent No. 2,154,629, issued April 18, 1939, to Edwin R. Littmann produces a modified rosin which may be used in the preparation of an alcohol derivative to be treated in accordance with this invention. Such modified rosins will hereinafter be termed Hyex rosins. The treatment of the I-Iyex rosin to produce an alcohol derivative produces an alcohol which is a mixture of the resin alcohols derived from the different components of the Hyex rosin as well as non-alcoholic impurities present. Similarly, I-Iyex treatment of a rosin alcohol gives a mixture of two or more chemically different substances.

The alcohol derivatives of modified rosins which I treat in accordance with this invention r may be the alcohol derivatives of modified rosins produced from any grade of wood or gum rosin which has been treated to modify its chemical structure so that the modified rosin resulting is a mixture of two or more chemically different materials. The alcohol derivatives of the modified rosins may be prepared from the modified rosins in any suitable manner such as by hydrogenation of the modified rosin under conditions which are satisfactory for alcohol formation. Alternatively, a rosin alcohol may be produced from rosin or a rosin ester by suitable hydrogenation treatment and the resulting rosin alcohol submitted to a treatment which will efiect a modification of the rosin nucleus of the rosin alcohol.

The selective solvent which I use in accordance with this invention may be any of the various selective solvents for the visible and latent color bodies of rosins and rosin esters heretofore known. Thus, I may use furfural, furfuryl alcohol, a chlorohydrin, as, ethylene chlorohydrin, propylene chlorohydrin, etc., aniline, phenol, resorcinol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, trimethylene glycol, glycerol, butyl glycerol, ethyl formate, methyl acetate, methyl formate, methyl orthonitrobenzoate, methyl furoate, alkyl formate, monoacetin, diacetin, triacetin, ethylene glycol monoacetate, methanol, hydroxyl alkyl amine,

- as triethanolamine, a solution of oxalic acid in water or in methanol, ethanol or other lower aliphatic alcohol, ethylene glycol monoethyl ether, or other immiscible glycol ether, ethylene glycol monoacetate, or other immiscible glycol ester, methyl thiocyanate, ethyl thiocyanate, acetonitrile, acetic acid, acetic anhydride, pchloroaniline, resorcinol plus hydrosulphite, ethylene glycol diacetate, glycerol diacetate, resorcinol monoacetate, resorcinol diacetate, phenyl acetate, furfuryl acetate, ethylidine cliacetate, n-propyl furoate, ethyl glycollate, methyl citrate, ethyl tartrate, ethyl malonate, methyl maleate, dimethyl phthalate, benzyl formate, monobutyrin, ethyl carbonate, methyl lactate, diethyl oxalate, methyl adipate, hydroxyhydroquinone triacetate, methyl chlorocarbonate, propylene glycol monoacetate, hydroquinone diacetate, catechol monoacetate, guaiacyl acetate, methyl glutarate, ethyl oxalate, benzyl acetate, diethyl glutacoate, ethyl lactate, diethyl phthalate, ethyl anisate, methyl salicylate, methyl cinnamate, methyl mandelate, methyl acrylate, ethyl oxamate, methyl succinate, ethyl propiolate, ethyl malate, methoxy-benzaldehyde, guaiacol, anisidin, nitroanisol, dichloroethyl ether, methoxy acetic acid, methyoxybenzyl alcohol, liquid sulfur dioxide, nitromethane, etc., or mixtures of such refining agents which are chemically non-reactive, etc.

The solvent in which I may dissolve the alcohol derivative of the modified rosin before contacting it with a selective solvent may be any solvent for the alcohol derivative of the modified rosin which is immiscible and non-reactive with the selective solvent used. Thus, I may use a petroleum hydrocarbon solvent, such as, for example, gasoline, petroleum ether, a normally gaseous petroleum hydrocarbon held in liquid phase by elevated pressure, low temperature, or both. The concentration of the alcohol derivative of the modified rosin in such a solution may be within the range of about 5% to about 80% by weight, and desirably within the range of about 15% to about 30% by weight.

The temperature at which the process in accordance with my invention may be carried out is dependent upon the selective solvent employed and will be within the range of about40 C. to about C. In any case the temperature used will be such that the selective solvent is a liquid under the pressure used.

In the embodiment of my process in which an alcohol derivative of a chemically modified rosin is dissolved in a solvent therefor before it is contacted with a selective solvent, the solution so formed may have aconcentration within the range of about 5% to about 40%, by weight. Usually I prefer to use a solution having a concentration within the range of about 10% to about 25% by weight.

The number of Washes employed in my process may be varied in accordance with the results desired, and it will be appreciated that the greater the number of washes given the sharper will be the separation of the components of the alcohol derivative of the chemically modified rosin treated.

As illustrations of the practical adaptation of the method in accordance with this invention, I

may cite the following:

EXAMPLE I The alcohol derivative of Hyex rosin was prepared by hydrogenation of Hyex rosin over a copper chromite catalyst at a temperature of 270-300 C. and a maximum hydrogen pressure of 2800 lbs/sq. in. Three portions of 160 grams each of a 25% solution of the alcohol in gasoline were counter-currently washed at room temperature (25 C.) with first a '70 cc. portion of furfural, then a 50 cc. portion followed by a 30 .cc. portion and four 25 cc. portions of furfural. The resulting gasoline solutions and the combined furfural washes were evaporated under reduced pressure to recover the components dissolved in each. The results obtained are given in Table I.

Table I Refractive index Add N 0' 1 Yield Hydroxyl Grade Percent Percent Original alcohol from Hyex rosin. Alcohol from gas.

sol. #1 Alcohol from gas.

s Alcohol from gas.

sol. Alcohol from combined furfural washes *By acctylation, corrected for acidity.

A comparison of the characteristics of the above table shows that the original alcohol has been separated into chemically different fractions by the furfural wash.

EXAMPLE II Table 2 Refractive index A cld NO Grade Hydroxyl* Yield Percent Percent Original alcohol from Hyex rosin Alcohol from gas.

sol. #1 Alcohol from gas.

sol. #2 Alcohol from gas.

sol. Alcohol from combin ed p hen o1 washes l. 5286 WW *By acetyla tion, corrected for acidity.

Inspection of the data of Table 2 shows that the original alcohol has been separated into different components having different characteristics. An alcohol of considerably higher purity was isolated from the combined phenol washes.

EXAMPLE III Three portions of 200 grams each of the 25% gasoline solution of the alcohol derived from Hyex rosin used in Example I were counter-currently washed at room temperature (25 C.) first with a cc. portion of methyl thiocyanate then with three successive 50 cc. portions followed by two 30 cc. portions of methyl thiocyanate. After each wash the solutions were cooled in an ice-bath to permit more complete separation of the methyl thiocyanate layer. The gasoline solutions and the combined methyl thiocyanate washes were evaporated under reduced pressure to recover the components dissolved in each. The characteristics of the products recovered from each of the solutions are shown in Table 3.

Table 3 Ref ractivzggrgex Hydroxyl N0 Grade Yield Original alcohol Percent Percent from Hyex rosin. l. 5393 4. 2 5. 0 H Alcohol from gas.

sol. 1. 5258 1. 4 4. 7 WW 5. 2 Alcohol from gas.

501. #2 l. 5322 2.6 5.4 WG 11.0 Alcohol from gas.

sol. #3 1.5355 3. 2 5.4 N 15. 1 Alcohol from combined methyl t h i o c y a n a t e washes l. 5433 4. 2 4. 9 H 68. 7

*By acetylation, corrected for acidity.

A comparison of the characteristics shown in Table 3 illustrates the separation of the original alcohol into chemically difierent components.

It will be understood that the above examples and details of operation are given by way of illustration only, and that the scope of my invention as herein broadly described and claimed is in no way limited thereby.

Wherein the appended claims I have used the term Hyex rosin alcohol it will be understood that I mean a rosin alcohol in which the rosin nucleus has undergone a chemical modification involving interand intra-molecular rearrangement within the hydrocarbon nucleus of the rosin as hereinbefore described.

This application forms a division of my application, Serial No. 296,946, filed September 28, 1939, entitled Method for the separation of chemically modified rosin alcohols into components, which is in turn a continuation-inpart of my application, Serial No. 160,725, filed August 24, 1937, entitled Method for the separation of chemically modified rosins and their esters into components, now U. S. Patent No, 2,191,306.

What I claim and desire to protect by Letters Patent is:

1. The method of separating a Hyex rosin alcohol into its components which comprises dissolving the Hyex rosin alcohol in a solvent therefor, contacting the solution so formed with a selective rosin color-body solvent immiscible with the said solution, separating the selective solvent therefrom and recovering a component of the Hyex rosin alcohol from each of the resulting solutions.

2. The method of separating a Hyex rosinalcohol into. its components which comprises dissolving the Hyex rosin alcohol in a solvent therefor, contacting the solution so formed with a selective resin color-body solvent immiscible with the said solution, separating the selective solvent therefrom and recovering a component of the Hyex rosin alcohol from each of the resulting solutions by evaporating the solvent.

3. The method of separating a Hyex rosin alcohol into its components which comprises dissolving the Hyex rosin alcohol in a solvent therefor, contactingjthe solution so formed with furfural, separating the furfural therefrom and recovering a component of the Hyex rosin alcohol from each of the resulting solutions by evaporating the solvent.

4. The method of separating a Hyex rosin alcohol into its components which comprises dissolving the Hyex rosin alcohol in a solvent therefor, contacting the solution so formed with phenol, separating the phenol therefrom and recovering a component of the Hyex rosin alcohol from each of the resulting solutions by evaporating the solvent.

5. The method of separating a Hyex rosin alcohol into its components which comprises dissolving the Hyex rosin alcohol in a solvent therefor, contacting the solution so formed with an alkyl thiocyanate, separating the alkyl thiocyanate therefrom and recovering a component of the Hyex rosin alcohol from each of the resulting solutions by evaporating the solvent.

6. The method of separating a Hyex rosin alcohol into its components which comprises dissolving the Hyex rosin alcohol in a petroleum hydrocarbon solvent, contacting the solution so formed with a selective rosin color-body solvent immiscible'with the said solution, separating the selective solvent therefrom and recovering a component of the Hyex rosin alcohol from each of the resulting solutions by evaporating the solvent.

7. The method of separating a Hyex rosin alcohol into its components which comprises dissolving the Hyex rosin alcohol in a petroleum hydrocarbon solvent, contacting the solution so formed With furfural, separating the furfural therefrom and recovering a component of the Hyex rosin alcohol from each of the resulting solutions by evaporating the solvent.

8. The method of separating a Hyex rosin alcohol into its components which comprises dissolving the Hyex rosin alcohol in a petroleum hydrocarbon solvent, contacting the solution so formed with phenol, separating the phenol therefrom and recovering a component of the Hyex rosin alcohol from each of the resulting solutions by evaporating the solvent.

9. The method of separating a Hyex rosin alcohol into its components which comprises dissolving the Hyex rosin alcohol in a petroleum hydrocarbon solvent, contacting the solution so formed with an alkyl thiocyanate, separating the alkyl thiocyanate therefrom and recovering a component of the Hyex rosin alcohol from each of the resulting solutions by evaporating the solvent. 10. The method of separating a Hyex rosin alcohol into its components which comprises dissolving the Hyex rosin alcohol in a solvent therefor, contacting the solution so formed countercurrently with a selective rosin color-body solvent immiscible with the said solution, separating the selective solvent therefrom and recovering a component of the Hyex rosin alcohol from each of the resulting solutions by evaporating the solvent.

JOSEPH N. BORGLIN. 

